EP0063855A1 - Flammfeste Polymerzusammensetzungen - Google Patents

Flammfeste Polymerzusammensetzungen Download PDF

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Publication number
EP0063855A1
EP0063855A1 EP82300429A EP82300429A EP0063855A1 EP 0063855 A1 EP0063855 A1 EP 0063855A1 EP 82300429 A EP82300429 A EP 82300429A EP 82300429 A EP82300429 A EP 82300429A EP 0063855 A1 EP0063855 A1 EP 0063855A1
Authority
EP
European Patent Office
Prior art keywords
composition according
brominated
aromatic component
brominated aromatic
chlorinated
Prior art date
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Granted
Application number
EP82300429A
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English (en)
French (fr)
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EP0063855B1 (de
Inventor
Charles S. Ilardo
Daniel J. Scharf
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Occidental Chemical Corp
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Occidental Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons

Definitions

  • This invention relates to flame retardant polyolefin compositions.
  • Polyolefin compositions are finding increasing use in a diversity of applications such as wire coatings, pipes, conduits, automotive products, marine products, fibers, coatings, industrial moldings, extensions, and various other products. These and other uses are often served by polyolefin compositions that are flame retardant. Many prior art attempts to impart fire retardance to such compositions by the use of additives have adversely affected the desirable properties of the polymer due to the high proportions of fire retardant additive often required to achieve an adequate level of fire retardancy. In addition, prior products have often been adversely affected, due to the migratory properties and sensitivity to environmental conditions of the fire retardant additives used.
  • This invention provides fire retardant polyolefin compositions containing additives that not only impart constant fire resistance but also enhance or preserve other physical properties of the protected composition.
  • polyolefin compositions are rendered flame retardant by incorporating therein 2-60 percent by weight of a synergistic combination of (1) a chlorinated organic component which is a compound of the formula wherein Y is selected from the group consisting of chlorine, fluorine, alkyl and aikoxy, Z is a tetravalent cyclic hydrocarbon having at least 4 carbon atoms, Z may be substituted by lower alkyl .of 1 to 6 carbon atoms, chlorine or fluorine.
  • the alkyl and alkoxy radicals mentioned generally have 1 to 10 carbon atoms and preferably are of 1 to 6 carbon atoms.
  • Z is a cyclic hydrocarbon of 5 to 18 carbon atoms and from 1 to 5 cyclic structures.
  • Z is a plurality of cyclic structures, they are fused, that is, share carbon atoms, and (2) a brominated aromatic component selected from the group consisting of ring brominated aromatic polyesters; aromatic anhydrides; aromatic imides; phenols; benzenes; naphthalenes; polyphenyls; and aromatic substituted poly alkylenes; wherein the chlorinated and brominated components are present in a ratio of about 10:1 to about 0.1:1.
  • Both the chlorinated and the brominated components described herein include various materials known to be useful as flame retardant additives for various compositions.
  • the combination of chlorinated and brominated components when incorporated in a polyolefin flame composition, acts in a synergistic fashion, to provide a suprisingly higher degree of flame retardance than comparable additive compositions of either component individually.
  • the compounds that may be employed as the chlorinated organic component of the synergistic flame retardant additives of this invention are Diels-Alder adducts of chlorinated cyclopentadiene. Generally such compounds will have a melting point above about 250 degrees Celsius, a vapor pressure of less than about 0.10 millimeters of mercury at 197 degrees Celsius and a chlorine content of at-least about 40 percent. Suitable compounds are described in detail in U. S. Patents 3,403,036 and 4,000,114, the disclosures of which is incorporated by reference herein.
  • Such compounds may be made by adduct- ing (Diels Alder reaction) one mole of a polyunsaturated cycloaliphatic or heterocyclic compound and two or more moles of a polyhalogenated cyclopentadiene of the formula X and Y have the same definition as previously stated.
  • the polyunsaturated cycloaliphatic compound mentioned above contains 5 to 18 carbon atoms, has 1 to 5 cyclic structures and when more than one, the cyclic structures are fused and at least two sites of carbon to carbon unsaturation which may be either ethylenic or acetylenic.
  • Illustrative of the polyhalogenated cyclopentadienes suitable for use in this invention are hexachlorocyclopentadiene, 5,5 - dimethoxytetrachlorocyclopentadiene, 5,5-difluorotetrachlorocyclopent diene, 5,5 - dibromotetrachlorocyclopentadiene, and 5,5-diethoxy- tetrachlorocyclopentadiene.
  • Satisfactory polyunsaturated aliphatic compounds for use in preparing the Diels-Alder adduct with include cycloaliphatic compounds exemplified by but not limited to methyl cyclopentadiene, cyclopentadiene, dicyclopentadiene, bicyclo(2.2.1)heptadiene, 1,5-cyclooctadiene, cyclodecadiene and cyclododecadiene.
  • Suitable polyunsaturated heterocyclic compounds include the furans and thiophenes.
  • the adduct is prepared by condensing two moles of hedachlorocyclopentadiene with one mole of 1,5-cyclooctadiene in xylene at a temperature below 200 degrees centigrade.
  • the adduct melts at above 350 degrees centigrade and has a vapor pressure of 0.006 millimeter of mercury at 197 degrees centigrade.
  • 1,2,3,4,5,6,7,8,10,10,11,11 - dodecachloro - 1, 4:5,8-dimethanofluorene is prepared by condensing two moles of hexachlorocyclopentadiene with one mole of cyclopentadiene.
  • This adduct has the assigned structure for convenience this adduct will be referred to as Cp.
  • CP melts at about 319 degrees centigrade to 322 degrees centigrade and has a vapor pressure of 0.031 millimeter of mercury at 197 degrees centigrade.
  • the adduct 1,2,3,4,5,6,7,8,12,12,13,13 - dodecachloro-1,4:5, 8:9,10-trimethano-anthracene is prepared by condensing one mole of the Diels-Alder adduct of cyclopentadiene and acetylene with two moles of hexachlorocyclopentadiene.
  • the resulting adduct has the assigned structure: For convenience this adduct will be referred to as BCH.
  • brominated aromatic component examples include ring brominated aromatic polyesters; aromatic anhydrides; aromatic imides; phenols; benzenes; naphthalenes; polyphenyls; and aromatic substituted polyalkylenes. Typical of such ring brominated aromatic compounds are the following:
  • Typical compounds of this class are monobromobenzene, pentabromobenzene, hexabromobenzene, tribromoanisole, tribromophenoxybenzene, pentabromochloro- benzene, and the like.
  • Typical compounds of this class include, for example, monobromonaphthalene; dibromonaphthalene; tribromonapthalene; tetra- bromonaphthalene; monobromoanthracene; dibromoanthracene; tribromo- anthracene; monobromophenanthrene; dibromophenanthrene; tetrabromo- phenanthrene and the like.
  • Typical compounds of this class include for example pentabromodiphenyl oxide, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, polydibromophenylene oxide, poly- bromobiphenyl, polybromopolyphenylene, polybromopolyphenyl methylene, and the like.
  • Typical compounds of this class include, for example, polyethylene (polybromo) terephthalate; polybutylene (polybromo) terephthalate; and the like.
  • Brominated imides such as those characterized by the formula where m is 1-4; and R is alkyl, phenyl, halophenyl, benzyl, halobenzyl, or a halogen substituted alkylene imido of the formula where m is 1-4 and q is greater than zero.
  • Typical compounds of this class include, for example, bis(tetrabromophthalimido)ethane; bis(tetrabromophthalimido)methane; N-phenyl tetrabromophthalimide.
  • R is as defined above; and R' is hydrogen, alkyl, hydroxyl alkyl, phenyl, benzyl, or a carboxylate linkage.
  • the latter is illustrative of a type of polycarbonate structure prepared by the reaction of brominated bisphenol A with phosgene.
  • Typical brominated bisphenols include for example, tetrabromo bisphenol A, and bis (hydroxyethyl ether) tetrabromo bisphenol A.
  • the polymeric compositions and coatings of this invention include high molecular weight polymers and resins as well as the intermediate molecular weight materials utilized for coatings and paints.
  • the polymers embraced within the scope of this invention include the homopolymers and copolymers of unsaturated aliphatic hydrocarbons, including, for example polyethylene, polypropylene, and ethylene/propylene copolymers.
  • the ⁇ polymers of the invention can be in various physical forms, such as shaped articles, for example, moldings, sheets, rods, and the like; fibers, coatings, films and fabrics, and the like.
  • polyethylene and polypropylene Two of the polymers that are particularly suitable for the fire retardant polymer compositions of this invention, polyethylene and polypropylene, are well known in the art.
  • Low-density (0.92 grams/cc.) polyethylene may be produced by the polymerization of ethylene at a pressure greater than twelve hundred atmospheres and at a temperature of one hundred to three hundred degrees centigrade. Lower pressures of about five hundred atmospheres can be used if a catalyst such as oxygen or benzoyl peroxide is added to the ethylene as described by Fawcett et al., Chemical Abstracts, 32, 1362 (1938).
  • the reaction is carried out in the presence of an inert hydrocarbon diluent, suitably purified of catalyst poisons, at a temperature in the range of fifty to two hundred and thirty degrees centigrade.
  • an inert hydrocarbon diluent suitably purified of catalyst poisons
  • the polymer can be recovered from the resulting solution of suspension by evaporation of the diluent, whereupon the polymer is treated for removal of catalyst residues, for example, by washing with water or alcohol and acids.
  • Metal oxide catalysts such as chromium oxide supported on silica or alumina, are suitable for polymerizing 1-olefins containing a maximum of eight carbon atoms, with no branching closer to the-double bond than the 4-position. Such polymerization may be carried out in the manner described for the organometallic catalyst system.
  • the chlorine-bromine containing additives of this invention may be incorporated into the polymer in a variety of ways.
  • the additives can be introduced into the polymer while the latter is dissolved in a suitable solvent. This procedure is especially useful when it is desired to mix the additives during the polymer manufacturing process.
  • the additives are intimately mixed with the polymer.
  • the additives are mixed with the polymer in the molten state at temperatures that can range from the melting point to the decomposition temperature of the polymer, e.g., from 70 to 600 degrees centigrade.
  • the additives and polymer are dry-blended in the finely-divided state so that an intimate mixture is obtained upon subsequent milling or extrusion.
  • the combination additive of the invention that is the combination of the chlorinated and brominated components is incorporated in the polymeric material in an effective fire retardant proportion.
  • the combination of halogenated components is incorporated in the amount of about 2 to about 60 percent by weight of the polymeric composition and desirably from about 5 to about 50 percent by weight of the polymer composition and preferably from about 10 to about 40 percent by weight of the total polymer composition.
  • the proportion of chlorinated and brominated components will vary depending on the particular compounds employed, but should provide a preferred weight ratio of chlorine:bromine of between about 10:1 and about 0.1:1 and most preferably about 3:1 to about 0.3:1.
  • Antimony oxide is the antimony compound that is presently preferred for use in the present invention.
  • Suitable antimony compounds include the sulfides of antimony, salts of the alkali metals of Group 1 of the Periodic Table, antimony salts of organic acids and their pentavalent derivatives and the esters of antimonius acids and their pentavalent derivatives. It is convenient to use sodium antimonite or potassium antimonite when it is desired to use an alkali metal salt of the antimony for compositions of this invention.
  • U. S. Patent 2,996,528 discloses suitable antimony salts of organic acids and their pentavalent derivatives.
  • Compounds of this class include antimony butyrate, antimony valerate, antimony caproate, antimony heptylate, antimony caprylate, antimony pelargonate, antimony caprate, antimony cinnate, antimony anisate, and their pentavalent dihalide derivatives.
  • Patent 2,993,924 such as tris(n-octyl) antimonite, tris(2-ethylhexyl) antimonite, tribenzyl antimonite, tris(beta-chloroethyl) antimonite, tris(beta-chloropropyl) antimonite, tris(beta-chlorobutyl) antimonite, and their pentavalent dihalide derivatives.
  • Still other suitable organic antimony compounds are the cyclic antimonites such as trimethylol propane antimonite, pentaerythritol antimonite and glycerol antimonite.
  • the corresponding arsenic and bismuth compounds can also be employed in particular the oxides of arsenic and bismuth.
  • Example 1 Following a similar procedure to that of Example 1 using varying proportions of components and replacing the 1,5 COD (used in Examples 1 to 5) by a diadduct of hexachlorocyclopentadiene and furan (HF - Examples 7 to 10) or BCH (Examples 12 to 15), a series of fire retardant polypropylene samples were prepared and tested, with the results as shown in Table 1, below:
  • P E test samples A series of cross-linked fire retardant polyethylene ( P E) test samples was prepared and tested following the procedure described above except that the composition was varied as shown in Table VI and the procedure was varied as follows: after mixing the fire retardant additives the polyethylene was treated with dicumyl peroxide curing agent in the amount of about 6.75 parts per 100 parts of fire retardant polyethylene and was then cross-linked and compression molded for 1/2 hour at 160°C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP82300429A 1981-04-24 1982-01-27 Flammfeste Polymerzusammensetzungen Expired EP0063855B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/257,082 US4388429A (en) 1981-04-24 1981-04-24 Flame retardant polymer compositions
US257082 1981-04-24

Publications (2)

Publication Number Publication Date
EP0063855A1 true EP0063855A1 (de) 1982-11-03
EP0063855B1 EP0063855B1 (de) 1987-07-15

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EP82300429A Expired EP0063855B1 (de) 1981-04-24 1982-01-27 Flammfeste Polymerzusammensetzungen

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US (1) US4388429A (de)
EP (1) EP0063855B1 (de)
JP (1) JPS57185334A (de)
AU (1) AU544931B2 (de)
CA (1) CA1195796A (de)
DE (1) DE3276759D1 (de)
ES (1) ES8306171A1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8500215A (pt) * 1984-01-30 1985-09-03 Occidental Chem Co Composicao de poliolefina retardantes de chama
US4829118A (en) * 1987-10-09 1989-05-09 Great Lakes Chemical Corporation Flame retardant ABS resin compositions
US4892892A (en) * 1987-10-09 1990-01-09 Great Lakes Chemical Corporation Flame retardant polyurethane foam compositions containing polynuclearbrominated alkylbenzene
US4831072A (en) * 1987-10-09 1989-05-16 Great Lakes Chemical Corporation Flame retardant MPPE resin compositions
KR890701677A (ko) * 1987-10-09 1989-12-21 죤 에스.리틀 내염성 pvc수지 조성물
US5008323A (en) * 1987-10-09 1991-04-16 Great Lakes Chemical Corporation Flame retardant PVC resin compositions
JPH01153742A (ja) * 1987-12-11 1989-06-15 Mitsubishi Plastics Ind Ltd 難燃性管状体
US4804698A (en) * 1988-04-04 1989-02-14 Ethyl Corporation Flame retardant polypropylene based formulations
US11739880B2 (en) 2021-05-19 2023-08-29 Samuel Gottfried High temperature protection wrap for plastic pipes and pipe appliances

Citations (2)

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US3723383A (en) * 1971-07-26 1973-03-27 Universal Oil Prod Co Novel flame retardant compositions of matter
US4000114A (en) * 1975-02-24 1976-12-28 Hooker Chemicals & Plastics Corporation Fire retardant polymer compositions with improved physical properties

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US2760947A (en) * 1953-02-24 1956-08-28 Dow Chemical Co Self-extinguishing alkenyl polymer compositions containing bromochloro compounds
GB1090598A (en) * 1964-08-17 1967-11-08 Hooker Chemical Corp Polymers and coatings rendered flame retardant by the addition of halogenated cyclopentadiene diels-alder adducts
NL148074B (nl) * 1964-09-25 1975-12-15 Gen Electric Werkwijze voor het oxydatief koppelen van dihalogeenfenolen.
US4581396A (en) 1968-09-18 1986-04-08 Raychem Corporation Flame retardants and compositions containing them
US3591507A (en) * 1969-07-23 1971-07-06 Phillips Petroleum Co Flame-resistant compositions comprising 1,2 bis(3,4-dibromocyclohexyl)-1,2-dibromoethane and antimony trioxide
US3632544A (en) * 1970-05-07 1972-01-04 Borg Warner Self-extinguishing polymeric compositions
US3828003A (en) * 1970-10-26 1974-08-06 Nippon Oils & Fats Co Ltd Flame resistant polymer compositions
US3699077A (en) * 1970-10-29 1972-10-17 American Cyanamid Co Combinations of phosphonium bromides and brominated aromatic compounds as flame-retardant compositions for olefin polymers
US3989531A (en) * 1971-08-05 1976-11-02 General Electric Company Fire-retardant polymeric compositions containing brominated biphenols
US3950456A (en) * 1972-08-18 1976-04-13 Cities Service Company Flame-retardant composition
DE2316204B2 (de) * 1973-03-31 1981-04-16 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zur Herstellung von 1,2-1,3- oder 1,4 - Bis - (brommethyl) - tetrachlorbenzolen und deren Verwendung als Flammschutzmittel
US4147741A (en) * 1976-01-27 1979-04-03 Standard Oil Company (Indiana) Anti-drip additive system for fire retardant polypropylene
US4101498A (en) * 1976-05-27 1978-07-18 Shell Oil Company Fire-resistant composition
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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723383A (en) * 1971-07-26 1973-03-27 Universal Oil Prod Co Novel flame retardant compositions of matter
US4000114A (en) * 1975-02-24 1976-12-28 Hooker Chemicals & Plastics Corporation Fire retardant polymer compositions with improved physical properties

Also Published As

Publication number Publication date
ES509737A0 (es) 1983-05-01
CA1195796A (en) 1985-10-22
AU7993482A (en) 1982-10-28
AU544931B2 (en) 1985-06-20
EP0063855B1 (de) 1987-07-15
JPS57185334A (en) 1982-11-15
ES8306171A1 (es) 1983-05-01
US4388429A (en) 1983-06-14
DE3276759D1 (en) 1987-08-20

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